EP3390469A1 - Procédé de réduction de l'isomérisation pendant la polymérisation et système pour le mettre en uvre - Google Patents

Procédé de réduction de l'isomérisation pendant la polymérisation et système pour le mettre en uvre

Info

Publication number
EP3390469A1
EP3390469A1 EP16831661.0A EP16831661A EP3390469A1 EP 3390469 A1 EP3390469 A1 EP 3390469A1 EP 16831661 A EP16831661 A EP 16831661A EP 3390469 A1 EP3390469 A1 EP 3390469A1
Authority
EP
European Patent Office
Prior art keywords
additive
olefin
reactor
heat exchanger
product stream
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP16831661.0A
Other languages
German (de)
English (en)
Inventor
Daniela Ferrari
Sean Ewart
Timothy Gambrel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of EP3390469A1 publication Critical patent/EP3390469A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/02—Recovery or working-up of waste materials of solvents, plasticisers or unreacted monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/14—Homopolymers or copolymers of vinyl fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/20—Homopolymers or copolymers of hexafluoropropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This disclosure relates to a method for a-olefin isomerization reduction during polymerization and to a system for accomplishing the same.
  • this disclosure relates to a method for isomerization reduction during the production of polyolefins.
  • FIG. 1 is a depiction of an exemplary process 10 that is presently used for producing a polyethylene copolymer that contains ethylene and octene.
  • the process 10 utilizes a reactor 12 into which reactants such as hydrogen, ethylene, octene, catalyst and solvent are added. During the reaction a portion of the octene added to the reactor is polymerized with the ethylene to form the copolymer which is then discharged along with any unreacted monomers and
  • a heat exchanger (HE) 14 disposed downstream of the reactor increases the temperature of the product stream before entering the devolatilizer 16.
  • HE heat exchanger
  • the isomerization of octene results in the formation of 2-octene, 3 -octene and 4- octene isomers that are inert to the polymerization process.
  • Water is added to the product stream upstream of the heat exchanger 14 and an anti-oxidant is added to the product stream downstream of the heat exchanger 14.
  • a devolatilizer 16 disposed downstream of the heat exchanger 14 removes any unreacted ethylene, solvent or octene and recycles it to the reactor 12 to undergo further polymerization.
  • the isomerization of octene to 2-octene, 3-octene and 4-octene isomers is undesirable because it reduces the yield of the copolymer.
  • a method for reducing isomerization during the copolymerization of ethylene with an a-olefin comprising adding to a reactor a reaction mixture comprising hydrogen, ethylene, an a-olefin, a solvent and a catalyst; where the catalyst does not include a chain shuttling agent that comprises dialkyl zinc; heating the reactor to a first temperature to react the ethylene with the a-olefin to form a copolymer; discharging from the reactor a first product stream to a heat exchanger; where the product stream comprises the copolymer; adding to the product stream prior to the heat exchanger a first additive that is operative to reduce isomerization of the a-olefin; and discharging from the heat exchanger a second product stream.
  • a method for reducing isomerization during the copolymerization of ethylene with 1 -octene comprising adding to a reactor a reaction mixture comprising hydrogen, ethylene, an a-olefin, a solvent, a first additive and a catalyst; where the catalyst does not include a chain shuttling agent that comprises dialkyl zinc; and where the first additive is operative to reduce isomerization of the a-olefin; heating the reactor to a first temperature to react the ethylene with the a-olefin to form a copolymer; discharging from the reactor a first product stream to a heat exchanger; where the product stream comprises the copolymer; and discharging from the heat exchanger a second product stream.
  • a system comprising a reactor that is operative to react a reaction mixture comprising hydrogen, ethylene, a solvent, an a-olefin, and a catalyst to form a polyethylene copolymer; where the catalyst does not include a chain shuttling agent that comprises dialkyl zinc; and_a heat exchanger that is operative to receive a product stream containing the polyethylene copolymer from the reactor in addition to receiving an additive that is operative to reduce isomerization of the a-olefin.
  • a system comprising a reactor that is operative to react a reaction mixture comprising hydrogen, ethylene, a solvent, an a-olefin, an additive and a catalyst to form a polyethylene copolymer; where the catalyst does not include a chain shuttling agent that comprises dialkyl zinc; and where the additive is operative to reduce isomerization of the a-olefin; and a heat exchanger that is operative to receive a product stream containing the polyethylene copolymer from the reactor.
  • Figure 1 is a depiction of an exemplary prior art process that is used for producing a polyethylene copolymer that contains ethylene and octene;
  • Figure 2 is a depiction of an exemplary process that reduces the isomerization of 1 -octene during the production of the polyethylene copolymer that contains ethylene and octene.
  • [001 1] Disclosed herein is a method for reducing the amount of isomerization of a- olefins that occur during the polymerization with ethylene to produce and ethylene copolymer. More specifically, disclosed herein is a method for reducing the amount of octene that is converted into 2-octene, 3-octene and 4-octene obtained during the production of a polyethylene copolymer.
  • the method comprises adding an additive upstream of the reactor and/or upstream of the heat exchanger that reduces octene isomerization and hydrogenation.
  • the additive is added upstream of only the heat exchanger and downstream of the reactor to reduce the isomerization of the a-olefin during the manufacturing of the ethylene copolymer.
  • FIG. 2 is a depiction of an exemplary embodiment of a process 100 for reducing the amount of undesirable a-olefin isomers.
  • the system 100 comprises a reactor 102 that is operative to receive reactants that produce a polyethylene copolymer.
  • the reactants are hydrogen, ethylene, an a-olefin, a catalyst and a solvent.
  • the catalyst is a molecular catalyst that does not include a chain shuttling agent that comprises zinc.
  • the catalyst is a molecular catalyst that does not include a chain shuttling agent that comprises dialkyl zinc.
  • a first additive that is operative to minimize isomerization of the a-olefin is also added to the reactor 102.
  • the system 100 further comprises a heat exchanger (HE) 104 and a devolatilizer 106 both of which lie downstream of the reactor 102 and are in fluid communication with the reactor 102.
  • the heat exchanger 104 is generally operated at a higher temperature than the reactor 102.
  • the devolatilizer 106 lies downstream of the heat exchanger 104 and is in fluid communication with it.
  • the heat exchanger 104 receives a first product stream that comprises a copolymer of ethylene and a-olefin along with unreacted reactants and other byproducts from the reactor 102.
  • Water and a second additive are added downstream of the reactor 102 and upstream of the heat exchanger 104.
  • the second additive is operative to reduce isomerization of the a-olefin during the heating in the heat exchanger 104.
  • the devolatilizer 106 receives a second product stream from the heat exchanger.
  • the term "second product stream” is used to distinguish the "first product stream” from the “second product stream” and is not meant to indicate that the devolatilizer 106 receives two product streams from the heat exchanger 104.
  • the temperature of the product stream leaving the heat exchanger 104 is greater than the temperature of the product stream entering the heat exchanger 104.
  • the first additive may be the same as the second additive or different from it. Both the first additive and the second additive reduce isomerization of the a-olefin during the polymerization process.
  • a third additive may be added downstream of the heat exchanger 104.
  • the third additive may be the same or different from the first additive and the second additive.
  • the first additive, the second additive and the third additive are the same additive and function to reduce isomerization of the a-olefin during the polymerization process.
  • the a-olefins that undergo isomerization in the absence of the additive are 1- butene, 1-hexene, 1 -octene, 1 -decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 - octadecene, or the like, or a combination thereof.
  • a preferred a-olefin is 1 -octene.
  • the additives that are added to the reactor 102 and the heat exchanger 104 comprise moieties that reduce isomerization of the a-olefins during the polymerization process.
  • moieties are hydroxyls, amines, carboxylic acids, esters of carboxylic acids, phosphates, fluorine, or a combination thereof.
  • Preferred additives that may be added to the reactor and/or to the product stream prior to or after the heat exchanger are aromatic species having one or more hydroxyl functionalities, amines (e.g.
  • fatty acids e.g., stearic acids
  • salts of fatty acids e.g. , stearates
  • esters of fatty acids or the like, or a combination thereof. It is desirable for the additives to avoid catalyst deactivation and participating in the polymerization of the ethylene with the a-olefins and thus becoming part of the copolymer.
  • Aromatic species having one or more hydroxyl functionalities may be used as the additive.
  • Aromatic species having the following structure shown in the formula (1) can be used:
  • Ri through 3 ⁇ 4 is a hydroxyl group, with the remainder of Ri through Ri being independently a hydrogen, a substituted or unsubstituted C 1 - C 15 alkyl group, a substituted or unsubstituted C 1 - C 15 cycloalkyl group, a substituted or unsubstituted C 1 - C 15 ester group, or a halogen group.
  • Examples or the aromatic species of the formula (1) that may be used as the additive are phenol, dihydroxybenzene (e.g., catechol, resorcinol and hydroquinone), trihydroxybenzene (e.g., hydroxyquinol, phloroglucinol, and pyrogallol),
  • dihydroxybenzene e.g., catechol, resorcinol and hydroquinone
  • trihydroxybenzene e.g., hydroxyquinol, phloroglucinol, and pyrogallol
  • alkylphenol e.g., cresols, xylenols, propylphenol, butylphenol, amylphenol, heptylphenol, octylphenol, nonylphenol, dodecylphenol and related "long chain alkylphenols" (LCAPs)
  • LCAPs long chain alkylphenols
  • Bisphenol-type dihydroxy aromatic compounds may also be used as the additive and may include some of the following: 4,4'-dihydroxybiphenyl, 1 ,6- dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4- hydroxyphenyl)diphenylmethane, 1 ,2-bis(4-hydroxyphenyl)ethane, 2-(4-hydroxyphenyl)-2- (3-hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3- bromophenyl)propane, 1 , 1 -bis(hydroxyphenyl)cyclopentane, 1 , 1 -bis(4- hydroxyphenyl)cyclohexane, 1 , 1 -bis(4-hydroxyphenyl)isobutene, 1 , 1 -bis(4- hydroxyphenyl)cyclodode
  • Exemplary phenols are Irganox 1010 commercially available from BASF and IRGANOX 1076 commercially available from Ciba.
  • Primary amines have one of three hydrogen atoms in ammonia is replaced by an alkyl or aromatic.
  • Examples of primary amines include methylamine, ethanolamine, octylamine, aniline, or the like, or a combination thereof.
  • Secondary amines have two organic substituents (alkyl, aryl or both) bound to the nitrogen atom of ammonia together with one hydrogen (or no hydrogen if one of the substituent bonds is a double bond).
  • Examples of secondary amines include dimethylamine and methylethanolamine, diphenylamine or the like, or a combination thereof.
  • tertiary amines all three hydrogen atoms are replaced by organic substituents. Examples include trimethylamine, triphenyl amine, trioctylamine, or the like, or a combination thereof.
  • Cyclic amines are either secondary or tertiary amines.
  • Examples of cyclic amines include the 3-member ring aziridine and the six-membered ring piperidine.
  • N- methylpiperidine and N-phenylpiperidine are examples of cyclic tertiary amines.
  • hindered amines Some of the aromatic secondary and tertiary amines listed above are termed hindered amines.
  • hindered amines are n,n'-bis(l,4-dimethylpentyl-p- phenylenediamine), alkylated diphenylamines, 4,4'-bis(alpha, alpha- dimethylbenzyl)diphenylamine, diphenyl-p-phenylenediamine, mixed di-aryl-p- phenylenediamines, l,8-bis(dimethylamino)naphthalene, N',N',N',N'-tetramethyl-l ,8- naphthalenediamiine, or the like, or a combination thereof.
  • hindered amines are CHIMASSORB 2020, CHIMASSORB 119, CHIMASSORB 994, and CGL 116
  • Additives that comprise carboxylic acid functional groups are useful for reducing the isomerization.
  • Fatty acids are a useful group of additives for use in the reactor and/or in the heat exchanger.
  • a fatty acid is a carboxylic acid with a long aliphatic tail (chain), which is either saturated or unsaturated. Most naturally occurring fatty acids have a chain of an even number of carbon atoms, from 12 to 28.
  • saturated fatty acids are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, or the like, or a combination thereof.
  • unsaturated fatty acids are myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, arachidonic acid,
  • the carboxylic acid groups present in the fatty acids can reduce isomerization of the a-olefin in the heat exchanger.
  • a preferred fatty acid for use in minimizing isomerization of a-olefins is stearic acid.
  • Salts and esters of fatty acids may also be used as additives.
  • Fatty acid salts of Group I and II metals are useful for reducing isomerization of the a-olefins.
  • Preferred salts of fatty acids are lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba) salts, or a combination thereof.
  • Potassium, sodium, calcium and magnesium salts of the fatty acids are more preferred.
  • potassium, sodium, calcium and magnesium salts of stearic acid are preferred.
  • Sodium stearate, potassium stearate, magnesium stearate, calcium stearate or a combination thereof are especially preferred as additives for minimizing the
  • esters of fatty esters are fatty acid alkyl esters. Fatty acid methyl esters and fatty acid ethyl esters are preferred.
  • Fluoropolymers may also be used as additives for minimizing the
  • fluoropolymers are polyvinyl fluoride,
  • polyvinylidene fluoride polytetrafluoroethylene, polychlorotrifluoroethylene,
  • the fluoropolymers may be homopolymers, block copolymers, random copolymers, star block copolymers, alternating copolymers, or combinations thereof. Combinations of the foregoing fluoropolymers can include blends of the fluoropolymers that are not reactively bonded to each other.
  • the fluoropolymers have weight average molecular weights (Mw) of 500 to 10,000, preferably 1 ,000 to 8,000 and more preferably 1 ,500 to 5,000 grams per mole (g/mole).
  • Mw weight average molecular weights
  • An exemplary commercially available fiuoropolymer is DYNAMAR 5920A commercially available from 3M Advanced Materials.
  • Phosphates may also be used as an additive to reduce isomerization.
  • Phosphates are salts of phosphoric acid H3PO4.
  • Phosphate salts having the structure of formula (2) may be used
  • Ri, R2 or R3 is hydrogen, and where the remainder of Ri, R2 or R3 are either metal ions, or organic groups that comprise a substituted or unsubstituted C 1 - C 15 alkyl group, or a substituted or unsubstituted C 1 - C 15 cycloalkyl group.
  • the salts can therefore be organic or inorganic salts.
  • Inorganic salts generally have the structure of formula (3) below:
  • M is sodium, calcium, potassium, rubidium, cesium, ammonium, or the like, and where one or more of Ri and R2 are hydrogen atoms.
  • two of the R groups i.e., any two of Ri, R2 or R3 and may be joined together to provide a cyclic group, for example, diphenyl pentaerythritol diphosphate.
  • Suitable phosphates can be aromatic phosphates, such as, for example, phenyl bis(dodecyl)phosphate, phenyl bis(neopentyl)phosphate, phenyl bis(3,5,5'-trimethylhexyl)phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p- tolyl)phosphate, bis(2-ethylhexyl)p-tolyl phosphate, tritolyl phosphate, bis(2- ethylhexyl)phenyl phosphate, tri(nonylphenyl)phosphate, bis(dodecyl)p-tolyl phosphate, di butyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5 '- trimethylhexyl)phosphate, 2-ethylhexyl diphenyl phosphate
  • Polymeric phosphates can also be used as additives.
  • Di- or polyfunctional aromatic phosphorus-containing compounds are also useful, for example, compounds of the formulas below:
  • each R4 is a hydroxyl, a hydrocarbon having 1 to 15 carbon atoms; a hydrocarbonoxy having 1 to 15 carbon atoms and n is 1 to 30.
  • suitable di- or polyfunctional aromatic phosphorus-containing compounds include the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl)phosphate of bisphenol-A ( and
  • the additives can be added in amounts of up to 5,000 parts per million (ppm), preferably 1 to 3,000 ppm and more preferably 10 to 2,000 ppm based on a total weight of the copolymer manufactured.
  • reactants such as hydrogen, ethylene, a-olefin, a catalyst, and a solvent are added to the reactor.
  • the reactor is generally operated at a temperature of 160 to 210°C.
  • An optional additive such as, for example, one of those listed above may be added to the first reactor along with the reactants.
  • the copolymer product along with any undesirable byproducts are removed from the devolatilizer while unreacted reactants are recycled back to the reactor to undergo further processing.
  • the amount of a-olefin isomerization is reduced by 10 to 100 percent, preferably by 30 to 70 weight percent as compared with a process where the additive is added downstream of the heat exchanger, all other factors remaining unchanged.
  • the additives were mixed with Isopar-E and added at a total flow rate of 2 pounds per hour. Shown in parenthesis is the actual flow rate for each additive in grams per hour (g/h). In the additive tank, water is also present to give a water flow rate of 0.26 g/h for all runs.
  • first, second, third, and the like may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, first element, component, region, layer or section discussed below could be termed second element, component, region, layer or section without departing from the teachings of the present invention.
  • an upstream device as used herein refers to a device producing a fluid output stream that is fed to a “downstream” device.
  • the “downstream” device is the device receiving the output from the "upstream” device.
  • a device may be both "upstream” and “downstream” of the same device in certain configurations, e.g. , a system comprising a recycle loop.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de réduction de l'isomérisation pendant la copolymérisation de l'éthylène avec une α-oléfine consistant à ajouter dans un réacteur un mélange réactionnel comprenant de l'hydrogène, de l'éthylène, une α-oléfine, un solvant et un catalyseur ; le catalyseur ne comprenant pas d'agent de transfert réversible de chaîne qui comprend du dialkylzinc ; à chauffer le réacteur jusqu'à une première température pour faire réagir l'éthylène avec la α-oléfine pour former un copolymère ; à évacuer un premier courant de produit du réacteur vers un échangeur thermique ; le courant de produit comprenant le copolymère ; à ajouter au courant de produit, avant qu'il n'atteigne l'échangeur thermique, un premier additif servant à réduire l'isomérisation de la α-oléfine ; et à évacuer un second courant de produit de l'échangeur thermique.
EP16831661.0A 2015-12-16 2016-12-14 Procédé de réduction de l'isomérisation pendant la polymérisation et système pour le mettre en uvre Pending EP3390469A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201562268074P 2015-12-16 2015-12-16
PCT/US2016/066735 WO2017106392A1 (fr) 2015-12-16 2016-12-14 Procédé de réduction de l'isomérisation pendant la polymérisation et système pour le mettre en œuvre

Publications (1)

Publication Number Publication Date
EP3390469A1 true EP3390469A1 (fr) 2018-10-24

Family

ID=57910106

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16831661.0A Pending EP3390469A1 (fr) 2015-12-16 2016-12-14 Procédé de réduction de l'isomérisation pendant la polymérisation et système pour le mettre en uvre

Country Status (3)

Country Link
US (1) US11192969B2 (fr)
EP (1) EP3390469A1 (fr)
WO (1) WO2017106392A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0193263A1 (fr) * 1985-01-28 1986-09-03 Du Pont Canada Inc. Réduction de l'isomérisation dans un procédé de polymérisation en solution d'alpha-oléfines
US20080281037A1 (en) * 2005-03-17 2008-11-13 Karjala Teresa P Adhesive and Marking Compositions Made From Interpolymers of Ethylene/Alpha-Olefins
US20110207903A1 (en) * 2010-02-19 2011-08-25 Fontaine Philip P Process for polymerizing an olefin monomer and catalyst therefor
WO2016191076A1 (fr) * 2015-05-28 2016-12-01 Dow Global Technologies Llc Procédé pour former des interpolymères d'éthylène/alpha-oléfine

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3139460A (en) 1961-07-13 1964-06-30 Diamond Alkali Co Inhibition of isomerization of organic compounds
US4634744A (en) * 1985-01-09 1987-01-06 Chemplex Company Method of catalyst deactivation
US4701504A (en) 1986-01-23 1987-10-20 Du Pont Canada Inc. Reduction of isomerization in solution process for polymerization of alpha-olefins
US4777229A (en) 1986-01-23 1988-10-11 Du Pont Canada Inc. Reduction of isomerization in solution process for polymerization of alpha-olefins
US5118757A (en) * 1990-03-26 1992-06-02 Shell Oil Company Polymer production
US6828395B1 (en) * 2003-10-15 2004-12-07 Univation Technologies, Llc Polymerization process and control of polymer composition properties
AU2007261565A1 (en) * 2006-06-20 2007-12-27 Dow Global Technologies Inc. Process for desactivating polymerization catalyst using phosphoric- or phosphonic acid salts and a catalyst deactivator
EP2035461A2 (fr) * 2006-06-20 2009-03-18 Dow Global Technologies Inc. Désactivation d'un catalyseur de polymères et neutralisation d'acides par des ionomères
EP2291445B1 (fr) * 2008-06-18 2023-09-13 Dow Global Technologies LLC Procédés pour maîtriser l'encrassement et améliorer des compositions
EP2691425B1 (fr) * 2011-03-28 2017-04-19 Dow Global Technologies LLC Procédé de production de copolymères d'éthylène/alpha-oléfine à résistance améliorée à l'état fondu et articles obtenus à partir de ceux-ci
WO2012166469A1 (fr) 2011-06-01 2012-12-06 Dow Global Technologies Llc Procatalyseurs multimétalliques de zeigler-natta et catalyseurs préparés à partir de ces derniers pour polymérisations d'oléfines
WO2013052308A1 (fr) * 2011-10-04 2013-04-11 Dow Global Technologies Llc Système et procédé de polymérisation d'oléfine
CN104039840B (zh) * 2011-12-31 2016-08-31 尤尼威蒂恩技术有限责任公司 用于聚烯烃聚合方法的连续性添加剂
CA2809718C (fr) 2013-03-15 2020-03-24 Nova Chemicals Corporation Utilisation energetique amelioree dans une installation de polymerisation en solution
BR112016002597B1 (pt) * 2013-08-19 2021-03-02 Dow Global Technologies Llc método para polimerizar um ou mais polímeros à base de etileno
CA2847814C (fr) * 2014-03-27 2021-09-28 Nova Chemicals Corporation Systeme de reacteur autonettoyant
CA2868640C (fr) * 2014-10-21 2021-10-26 Nova Chemicals Corporation Procede de polymerisation de solution
KR101679515B1 (ko) * 2015-02-12 2016-11-24 주식회사 엘지화학 올리고머화 촉매계의 제조방법 및 이에 의해 제조된 올리고머화 촉매계

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0193263A1 (fr) * 1985-01-28 1986-09-03 Du Pont Canada Inc. Réduction de l'isomérisation dans un procédé de polymérisation en solution d'alpha-oléfines
US20080281037A1 (en) * 2005-03-17 2008-11-13 Karjala Teresa P Adhesive and Marking Compositions Made From Interpolymers of Ethylene/Alpha-Olefins
US20110207903A1 (en) * 2010-02-19 2011-08-25 Fontaine Philip P Process for polymerizing an olefin monomer and catalyst therefor
WO2016191076A1 (fr) * 2015-05-28 2016-12-01 Dow Global Technologies Llc Procédé pour former des interpolymères d'éthylène/alpha-oléfine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2017106392A1 *

Also Published As

Publication number Publication date
US20190023823A1 (en) 2019-01-24
US11192969B2 (en) 2021-12-07
WO2017106392A1 (fr) 2017-06-22

Similar Documents

Publication Publication Date Title
US10167348B2 (en) Solution polymers formed from methylene malonate monomers, polymerization, and solution polymer products
EP3243849A3 (fr) Procédés de polymérisation comprenant des distributions d'éthylène frais pour la préparation de polymères à base d'éthylène basse densité
US10450246B2 (en) Compositions for control and inhibition of polymerization of vinyl aromatic monomers, and methods of use thereof
TW467931B (en) Stabilizer mixtures
US11192969B2 (en) Method for isomer reduction during polymerization and system for accomplishing the same
TW201109344A (en) Solid alkylaryl phosphite compositions and methods for manufacturing same
CN104302602A (zh) 用于控制及抑制芳香族乙烯基单体的聚合的改良添加组合物及其使用方法
JP2017519072A (ja) ペレット化ポリマー組成物を生成するための改善されたプロセス
CN108137467A (zh) 用于合成丙烯酸低聚物的方法
US11390697B2 (en) Methods of polyolefin solids recovery
JP6370400B2 (ja) 溶融重合ポリカーボネートクエンチング
US11390698B2 (en) Methods of polyolefin solids recovery
TW570939B (en) Process for preparing polycarbonate
EP1423452B1 (fr) Procede de preparation de polycarbonates
TWI259191B (en) Method for preparing polycarbonate resin
CN112639019A (zh) 树脂组合物及其成型体
WO2016131747A1 (fr) Procédé de production de polycarbonates par transestérification de dithiocarbonates ou d'analogues de sélénium de ceux-ci avec des bisphénols
KR101916277B1 (ko) 용융 폴리카보네이트의 켄칭 방법
RU2667914C2 (ru) Система и способ для получения интерполимера пропилена и бутилена
KR20190132647A (ko) 모노머의 중합을 제어 및 억제하기 위한 조성물, 및 이의 사용 및 제조 방법
CN111170833A (zh) 一种酚类邻位甲基化反应抑制芳基甲基醚产生的方法
US11220593B2 (en) Propylene copolymer composition
JP5330811B2 (ja) ポリカーボネートおよび光学材料
US10196334B2 (en) Process for the alkylation of phenols
RU2500660C1 (ru) Композиция, ингибирующая полимеризацию при переработке жидких продуктов пиролиза, способ ее получения и способ ингибирования полимеризации при переработке жидких продуктов пиролиза

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180711

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20191128

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: DOW GLOBAL TECHNOLOGIES LLC

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230526

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20231206

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTC Intention to grant announced (deleted)
INTG Intention to grant announced

Effective date: 20240402

INTG Intention to grant announced

Effective date: 20240402